JPH11300210A - Catalytic composition for hydrocarbon fluid catalytic cracking - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve a metal resistance and a sulfur oxide catching capability by being used for fluid catalytic cracking of a hydrocarbon by a method wherein a catalytic composition is prepared by dispersing a crystalline aluminosilicate zeolite and a compound containing manganese and zinc in an inorganic matrix. SOLUTION: A catalytic composition to be used for fluid catalytic cracking of a heavy hydrocarbon containing a hydrocarbon, especially a metallic contaminant of nickel vanadium, etc., and a sulfur compound, is prepared by dispersing a crystalline aluminosilicate zeolite and a compound containing manganese and zinc in an inorganic matrix. As the compound containing manganese and zinc, any one of mixtures of manganese oxide and zinc oxide, a composite oxide of a manganese and a zinc, and a composite oxide of a manganese oxide and/or a zinc oxide, is preferable. Further, the compound containing manganese and zinc is preferably granular, 60 μm or under in an average particle size and of an oxide particle capable of being detected with X-ray.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons, and more particularly, to the flow of hydrocarbons, especially heavy hydrocarbons containing metal contaminants such as nickel and vanadium and sulfur compounds. Used for catalytic cracking, excellent in metal resistance, excellent sulfur oxide trapping ability, high activity, gasoline and middle distillate (LCO) selectivity, excellent residual oil (bottom) decomposition, and lower octane number (RON) The present invention relates to a catalyst composition for fluid catalytic cracking of hydrocarbons having a low content.

[0002]

BACKGROUND ART Conventionally, in the fluid catalytic cracking of heavy hydrocarbons containing metal contaminants such as nickel and vanadium, the crystal structure of crystalline aluminosilicate zeolite in which vanadium deposited on a catalyst is an active component is used. Destroy
It is known to cause a significant reduction in the activity of the catalyst,
In order to inactivate metal contaminants such as vanadium deposited on the catalyst, various catalysts containing various compounds as a metal scavenger to improve metal resistance have been proposed. (For example, JP-A-61-149241,
(See JP-A-62-38242)

[0003] However, although alkaline earth metal compounds have an excellent effect of inactivating metal contaminants,
In a catalyst composition in which an alkaline earth metal compound is dispersed as a metal scavenger in an inorganic oxide matrix, the alkaline earth metal migrates during the catalytic cracking reaction and reduces the thermal stability of the crystalline aluminosilicate zeolite. To destroy the crystal structure and reduce the activity of the catalyst. Alternatively, the alkaline earth metal is ion-exchanged into the crystalline aluminosilicate zeolite and is incorporated into the gasoline product obtained by the catalytic cracking reaction. ) Decreased.

Further, depending on the type of alkaline earth metal used as a metal scavenger, the alkaline earth metal is eluted when mixed with the inorganic oxide matrix precursor,
There is a problem that the properties of the obtained catalyst composition are adversely affected by ion exchange with the crystalline aluminosilicate zeolite or reaction with the inorganic oxide matrix precursor.

[0005] For this reason, the present applicant has solved the above problems by making alumina exist in the catalyst in a block shape or treating the catalyst with an aqueous solution containing phosphate ions during the production of the catalyst. A method for producing a catalyst composition for hydrocarbon fluid catalytic cracking in which the disadvantages of alkaline earth metals are improved without impairing the advantages of alkaline earth metals as scavengers has been proposed (Japanese Patent Publication No. 5-16908).
JP-A-4-200744).

On the other hand, when the catalytic cracking of hydrocarbons containing sulfur compounds, there is the combustion gas containing SO _X is discharged from the regenerator fluidized catalytic cracking (FCC) unit. Therefore, (JP-B-56-9196) a method for reducing the SO _X component in the combustion gas and, also been proposed a low SO _X reduction is possible catalyst composition (JP 56-111047 JP) I have.

In the above-mentioned method for reducing the SO _X component in the combustion gas, first, a sulfur compound in heavy hydrocarbons is attached to a catalyst together with coke, and the SO 2 is reacted in a regeneration tower of an FCC unit by the following reaction. After being changed to _X , it is reacted with a metal oxide to form a sulfate, which is captured in the catalyst.

S + O _{2 in} coke → SO ₂ + SO ₃ 2SO ₂ + O ₂ → 2SO ₃ Metal oxide (MO) + SO ₃ → MSO ₄

Next, in the reaction tower, the metal sulfate is changed into 2MSO ₄ + 8H ₂ → MS + MO + H ₂ S + 7H ₂ O sulfide by the following reaction, and hydrogen sulfide is released.

The sulfide releases hydrogen sulfide by the following reaction in the stripper. MS + H ₂ O → MO + H ₂ S The released hydrogen sulfide is collected together with the reaction product gas, and removed by amine washing. As a result, the SO _X component in the combustion gas of the regeneration tower decreases.

By the way, manganese oxide is known to have a sulfur oxide trapping performance (for example, Japanese Patent Publication No.
No. 6-9196), such a catalyst for fluid catalytic cracking of hydrocarbons may use such a manganese oxide supported on the catalyst. However, a catalyst composition supporting a manganese oxide by a method of contacting (including impregnation or ion exchange) a solution containing a manganese component with a catalyst is used during the preparation of the catalyst composition or the catalytic cracking reaction with a hydrocarbon. In addition, manganese is ion-exchanged and incorporated into the crystalline aluminosilicate zeolite, and the octane value (RON) of the gasoline product obtained by the catalytic cracking reaction is lowered.

In order to solve the above-mentioned problems, the present applicant has disclosed in Japanese Patent Laid-Open No. 7-323229,
A catalyst composition for hydrocarbon fluid catalytic cracking, characterized in that a crystalline aluminosilicate zeolite and a particulate manganese compound are dispersed in an inorganic oxide matrix, has been proposed.

Although such a catalyst composition for fluid catalytic cracking of hydrocarbons shows excellent effects in terms of metal resistance, sulfur oxide trapping ability, etc., it is further improved in terms of bottom resolution, middle distillate yield and the like. Some improvement was desired.

[0014]

SUMMARY OF THE INVENTION The present invention is used for fluid catalytic cracking of hydrocarbons, especially metal contaminants such as nickel and vanadium, and heavy hydrocarbons containing sulfur compounds to improve metal resistance and sulfur oxide trapping ability. Excellent, high activity, excellent gasoline and middle distillate (LCO) selectivity, and octane number (RON)
It is an object of the present invention to provide a catalyst composition for hydrocarbon fluid catalytic cracking, which has a small decrease in water content and further has excellent residua (bottom) cracking properties.

[0015]

The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention is characterized in that (i) a crystalline aluminosilicate zeolite and (ii) a compound containing manganese and zinc are dispersed in an inorganic matrix. Features.

The compound (ii) containing manganese and zinc is a mixture of manganese oxide and zinc oxide, a composite oxide of manganese and zinc, a mixture of manganese oxide and / or a mixture of zinc oxide and the composite oxide. It is preferable that it is either.

The compound (ii) containing manganese and zinc is preferably in the form of particles and has an average particle diameter of 60 μm or less. Furthermore, the (ii) compound containing manganese and zinc is preferably an oxide particle that can be detected by X-ray.

The catalyst composition for fluid catalytic cracking of a hydrocarbon according to the present invention preferably further contains activated alumina. The catalyst composition for fluid catalytic cracking of a hydrocarbon according to the present invention comprises: (i) a crystalline aluminosilicate zeolite: 5 to 50% by weight; and (ii) a compound containing manganese and zinc: 0.1 to 50% by weight. iii) Inorganic matrix: preferably having a component composition in the range of 20 to 94.9% by weight.

[0019]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention comprises (i) a crystalline aluminosilicate zeolite (hereinafter sometimes referred to as zeolite) and (ii) a compound containing manganese and zinc dispersed in an inorganic matrix. It is characterized by having.

The crystalline aluminosilicate zeolite (i) used in the present invention includes synthetic zeolites such as X-type zeolite, Y-type zeolite, mordenite, ZSM-type zeolite, and natural zeolites.
These are used in the form of being ion-exchanged with cations selected from hydrogen, ammonium and polyvalent metals, as in the case of ordinary catalytic cracking catalyst compositions. Among them, Y-type zeolite has high gasoline selectivity, and particularly, ultra-stable Y-type zeolite (USY) is preferable because it has excellent hydrothermal stability.

The compound (ii) containing manganese and zinc used in the present invention includes a mixture of manganese oxide and zinc oxide, a composite oxide of manganese and zinc, a manganese oxide and / or a zinc oxide. A mixture of composite oxides and the like can be given. The mixture of manganese oxides of manganese oxide and zinc _{oxide, MnO, Mn 2 O 3,} MnO 2, M
An oxide such as n ₃ O ₄ and a composite oxide containing manganese such as MnSiO ₃ are exemplified. As zinc oxide, Z
Examples thereof include oxides such as nO and ZnO ₂ and composite oxides containing zinc such as ZnFe ₂ O ₄ . Complex oxides of manganese and zinc As complex oxides of manganese and zinc, ZnMn ₂ O ₄ , Z
Mn-Zn composite oxides such as nMn ₂ O ₃ , Zn ₂ MnO ₄ , ZnMn ₃ O ₇ , and Zn ₂ Mn ₃ O ₈ are mentioned.

Further, in the present invention, ZnMn (SO ₄ ) ₂ , ZnMn (PO ₄ ) ₂ , ZMn
n ₂ MnSi ₂ O _7, Li may be used a composite oxide containing elements other than Mn-Zn such as ₂ ZnMn ₃ O _8. Further, in the present invention, a mixture of a manganese oxide, a zinc oxide, and a composite oxide such as the above-described Mn-Zn composite oxide, a composite oxide containing Zn, and a composite oxide containing Mn. Can also be used.

The compound containing manganese and zinc used in the present invention has a weight ratio of 95: 5 to 5: 5 as manganese oxide (MnO ₂ ) and zinc oxide (ZnO).
Compounds mixed in the range of 95, preferably 85:15 to 15:85 are desirable.

In the present invention, as such a compound containing (ii) manganese and zinc, a slag and a crushed product of a used dry battery can be used. Such processed products are
It is preferable from the viewpoint of effective utilization of resources if manganese oxides, zinc oxides, and composite oxides thereof are used and these are used as the compound source containing manganese and zinc of the present invention.

The compound (ii) containing manganese and zinc used in the present invention is preferably in the form of particles. When the compound containing manganese and zinc is in the form of particles, since the compound containing manganese and zinc is present in the form of blocks in the catalyst particles, the metal capturing ability without detrimental effects on the crystalline aluminosilicate zeolite and the removal of SO _X Performance can be enhanced.

The average particle diameter of the particulate compound (ii) containing manganese and zinc is preferably 60 μm or less, and more preferably 0.1 to 30 μm. When the average particle diameter is smaller than 0.1 μm, trapped metal contaminants such as vanadium are dispersed in the catalyst particles, so that the metal contaminants may not be sufficiently deactivated. On the other hand, if the average particle size exceeds 60 μm, it is not desirable as a catalyst for a fluidized bed in relation to the average particle size of the final catalyst composition.

The compound (ii) containing manganese and zinc is preferably an oxide particle which can be detected by X-ray. When the compound is an X-ray detectable oxide particle, manganese and zinc hardly migrate during catalyst preparation or catalytic cracking reaction use, and manganese and zinc are ion-exchanged and incorporated into zeolite. Octane number (RON) of the gasoline product obtained by the catalytic cracking reaction is small.

The (iii) inorganic oxide matrix used in the present invention is used for a usual catalyst for catalytic cracking,
Silica, silica-alumina, alumina, silica-magnesia, alumina that can also act as a binder
-Magnesia, phosphorus-alumina, silica-zirconia, silica-magnesia-alumina and other matrix components are exemplified. In addition, such matrix components include:
Clay minerals such as kaolin, halloysite, and montmorillonite may be included.

The catalyst composition for fluid catalytic cracking of a hydrocarbon according to the present invention comprises (i) 5 to 50% by weight, preferably 5 to 40% by weight of a crystalline aluminosilicate zeolite;
i) It is preferable that the compound containing manganese and zinc is dispersed in the inorganic matrix in the range of 0.1 to 50% by weight, preferably 0.5 to 20% by weight.

(I) When the amount of the crystalline aluminosilicate zeolite is less than 5% by weight, the resulting catalyst has low activity,
When the gasoline yield is low, and when it is higher than 50% by weight, the activity is too high and the gas and coke production is increased, so that the gasoline yield may be low.

If the content of the compound containing manganese and zinc is less than 0.1% by weight, the desired effect may not be obtained, and if it exceeds 50% by weight, the abrasion resistance of the catalyst composition may be reduced. (Attr.Res.) May decrease.

In the catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention, (iii) the inorganic oxide matrix is
It is desirably contained in the range of 0 to 94.9% by weight, preferably 30 to 90% by weight. The above (i) to (iii)
The weight percentages of the components are determined within the respective ranges so as to add up to 100% by weight.

Furthermore, in the catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention, other metal scavengers may be contained in the component (iii). As such a metal trapping agent, known ones are exemplified, and activated alumina is particularly preferable.

(Iv) When activated alumina is contained as a metal scavenger in the catalyst composition for hydrocarbon fluid catalytic cracking,
The following effects of the catalyst composition are further increased. SO removal
_X ability improves.

Increase the catalytic activity. Hydrothermal resistance is improved. The metal capturing ability is improved.

By having the above-mentioned effects,
Gasoline selectivity is improved, and gasoline yield is increased.
Further, as described in Japanese Patent Publication No. 5-16908 filed by the present applicant, such activated alumina may be composed of one or more metal components selected from alkaline earth metals and rare earth metals, and phosphorus. Components may be included.

The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention further comprises a rare earth element (also referred to as RE).
May be carried. Note that, as the rare earth element, one containing lanthanum as a main component, one containing cerium as a main component, one containing lanthanum or cerium as a main component, and the like are usually used. The amount of the rare earth (RE) contained in the hydrocarbon fluid catalytic cracking catalyst composition is 0.1 to 20 parts by weight, when the total of the components (i) to (iii) is 100 parts by weight,
Preferably, it is in the range of 0.5 to 10 parts by weight. When such a rare earth element is contained, the activity of the catalyst composition for fluid catalytic cracking of hydrocarbons can be improved.

The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention comprises a crystalline aluminosilicate zeolite and a compound containing manganese and zinc, together with activated alumina, if necessary, together with an inorganic oxide matrix precursor. It can be manufactured by mixing and spray drying.

Specifically, the above-mentioned (i) crystalline aluminosilicate zeolite and (ii) a compound containing manganese and zinc are added to a precursor of the above-mentioned inorganic oxide matrix, for example, silica hydrosol, silica-alumina hydrogel or the like. And uniformly mixed, and the resulting mixture slurry is spray-dried by a conventional method. Also,
The spray-dried particles may then be washed with water if desired, and furthermore, at the time of washing, rare earth chloride (RECl ₃ )
After the treatment with the solution, the rare earth (RE) may be supported by drying and firing again.

The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention is particularly suitable for use in fluid catalytic cracking of sulfur compounds and heavy hydrocarbons containing metal contaminants such as nickel and vanadium. However, it can also be used for catalytic cracking of hydrocarbons containing no metal contaminants. For catalytic cracking of hydrocarbons using the hydrocarbon fluid catalytic cracking catalyst composition according to the present invention, ordinary catalytic cracking conditions are employed.

The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention can be used for catalytic cracking of a wide range of petroleum fractions from kerosene / light oil to high-boiling deasphalted oil.

[0042]

Industrial Applicability The catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention has high metal resistance and hydrothermal stability, high activity, and a small decrease in activity. Also, the octane number of the gasoline produced is hardly reduced.

Further, when the catalyst composition for fluidized fluid catalytic cracking according to the present invention is used, hydrogen, coke,
The amount of dry gas generated can be reduced, and the liquid yield of gasoline and light cycle oil (LCO) can be increased.

Further, the catalyst composition for fluid catalytic cracking of hydrocarbons according to the present invention has a high ability to remove SO _X, so that the amount of SO _{X in} the exhaust gas can be reduced.

[0045]

The present invention will be described below with reference to examples.
The present invention is not limited thereby.

[0046]

Reference Example 1 Manganese-Zinc Compound Particles In this example, a commercially available manganese-zinc compound (trade name “IZET-CALSIGN” manufactured by Nomura Kosan Co., Ltd.) was used as the manganese-zinc compound. This manganese-zinc compound is a particle containing manganese oxide, zinc oxide, iron oxide and a composite oxide thereof, and contains manganese.
It contains 50.4% by weight in terms of MnO ₂ and 43.6% by weight of zinc in terms of ZnO, and further contains small components such as iron, and its oxides are mainly composed of ZnMn ₂ O ₄ , ZnMnO ₃ , ZnO, ZnFe ₂ O ₄ , Mn
O, Mn ₂ O ₃ , and Fe ₂ O ₃ .

FIG. 1 shows an X-ray diffraction diagram of the manganese-zinc compound particles. The average particle size of the manganese-zinc compound particles was 3 μm. Properties of dimanganese trioxide In the comparative example, dimanganese trioxide was used. This dimanganese trioxide was prepared by calcining a commercially available electrolytic manganese dioxide powder in air at 750 ° C. for 15 hours. This dimanganese trioxide is disclosed in Japanese Unexamined Patent Publication No. 7-323229.
As disclosed in Japanese Unexamined Patent Application Publication No. 2000-209, it is known as a catalyst for catalytic cracking of hydrocarbons which has excellent sulfur oxide trapping ability and metal resistance and has a small decrease in octane number (RON) of produced gasoline.

The manganese content of the dimanganese trioxide powder was 91.8% by weight in terms of Mn ₂ O ₃ , and the average particle size was 31.8%.
μm. FIG. 2 shows an X-ray diffraction diagram of the dimanganese trioxide powder.

[0049]

Example 1 12.5% by weight prepared by adding water glass to sulfuric acid
1387.5 g (dry basis) of kaolin clay, 75 g (dry basis) of activated alumina, and ammonium ion-exchanged at an exchange rate of 90% were added to 4000 g of a silica hydrosol containing SiO _2.
Type crystalline aluminosilicate (USY zeolite) 500g
(Dry basis), and the manganese-zinc compound 37.5g
(Dry basis) was added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Then, the fine spherical particles are washed with warm water, and a chloride (RECl ₃ ) solution of a rare earth (specifically, a mixed rare earth containing lanthanum and cerium as a main component, the same applies hereinafter) is reduced to 1.2% by weight in terms of RE ₂ O _3. After the addition, RE was supported and dried to obtain a hydrocarbon fluid catalytic cracking catalyst composition (A).

The catalyst composition for fluid catalytic cracking (A) obtained was composed of 3% by weight of activated alumina, 20% by weight of USY zeolite, 1.5% by weight of a manganese-zinc compound, RE ₂ O ₃
Was contained in an amount of 1.2% by weight, and the average particle size was 65 μm. Table 1 shows the properties of such a catalyst composition for fluid catalytic cracking.

[0051]

EXAMPLE 2 1300 g (dry basis) of kaolin clay, 75 g (dry basis) of activated alumina, and ammonium ion at an exchange rate of 90% were added to 4000 g of a silica hydrosol containing 12.5% by weight of SiO ₂ prepared by adding water glass to sulfuric acid. Exchanged y
Type crystalline aluminosilicate (USY zeolite) 500g
(Dry basis) and the manganese-zinc compound 125g
(Dry basis) was added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Next, the microspherical particles are washed, and a rare earth chloride (RECl ₃ ) solution is added thereto in an amount of 1.2% by weight in terms of RE ₂ O ₃ (on an oxide basis) to carry RE and then dried. Thus, a catalyst composition (B) for catalytic cracking of a hydrocarbon was obtained.

The obtained catalyst composition for fluid catalytic cracking (B) was prepared by adding 3% by weight of activated alumina and USY zeolite.
20% by weight, 5% by weight of manganese-zinc compound, RE ₂ O ₃
It was contained in an amount of 1.2% by weight, and the average particle size was 65 μm. Table 1 shows the properties of such a catalyst composition (B) for fluid catalytic cracking.

[0053]

[Comparative Example 1] 1387.5 g (dry basis) of kaolin clay, 75 g (dry basis) of activated alumina, and ammonium with an exchange rate of 90% were added to 4000 g of a silica hydrosol containing 12.5% by weight of SiO ₂ prepared by adding water glass to sulfuric acid. Ion exchanged Y
Type crystalline aluminosilicate (USY zeolite) 500g
(Dry basis) and 37.5 g (dry basis) of the above-mentioned dimanganese trioxide were added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Next, the microspherical particles are washed, and at the time of washing, rare earth chloride (RECl ₃ )
The solution was added to a concentration of 1.2% by weight in terms of RE ₂ O ₃ ,
, And dried to obtain a catalyst composition (C) for hydrocarbon fluid catalytic cracking.

The obtained catalyst composition (C) for fluid catalytic cracking of hydrocarbons comprises 3% by weight of activated alumina, 20% by weight of USY zeolite, 1.5% by weight of dimanganese trioxide, and RE ₂ O ₃ . It was contained in an amount of 1.2% by weight, and the average particle size was 65 μm. Table 1 shows the properties of such a catalyst composition for fluid catalytic cracking (C).

[0055]

Comparative Example 2 1300 g (dry basis) of kaolin clay, 75 g (dry basis) of activated alumina, 4000 g of silica hydrosol containing 12.5% by weight of SiO ₂ prepared by adding water glass to sulfuric acid, ammonium ion at 90% exchange rate Exchanged Y
Type crystalline aluminosilicate (USY zeolite) 500g
(Dry basis) and 125 g of the above-mentioned dimanganese trioxide (dry basis) were added to prepare a mixed slurry, and the mixed slurry was spray-dried to obtain fine spherical particles. Next, the fine spherical particles are washed, and at the time of washing, rare earth chloride (RECl ₃ )
The solution was added to a concentration of 1.2% by weight in terms of RE ₂ O ₃ ,
, And dried to obtain a catalyst composition (D) for hydrocarbon fluid catalytic cracking.

The obtained catalyst composition (D) for fluid catalytic cracking of hydrocarbons was composed of 3% by weight of activated alumina, 20% by weight of USY zeolite, 5% by weight of dimanganese trioxide and 1.20% of RE ₂ O ₃ .
It was contained in an amount of 2% by weight, and the average particle size was 65 μm. Table 1 shows the properties of such a catalyst composition (D) for fluid catalytic cracking of hydrocarbons.

[0057]

[Table 1]

[0058]

EXAMPLES 3-4, COMPARATIVE EXAMPLES 3-4 Performance test The catalyst compositions A, B, C, and D prepared in Examples 1 and 2 and Comparative Examples 3 and 4 were obtained using a catalyst circulation regeneration type Midget-2.
Performance evaluation was performed using a pilot plant.

A schematic diagram of the Midget-2 pilot plant is shown in FIG. In FIG. 3, 1 is a reactor, 2 is a stripper, 3 is a catalyst regenerator, 4 is a condenser, 5 is a fractionator, 6 is a receiver, 7 is a cat trap, 8 is a separator, 9 is a movable tube, 10 Is an air-cooled tube, 11 is
N ₂ inlet, 12 a raw material oil introduction port, 13 N _2, H ₂ O outlet 14 N ₂ inlet, 15 an air inlet 16 is in the transport tube, 17 the flue gas outlet .

The reaction in the reactor 1 is 2MSO ₄ + 8H ₂ → MS + MO + H ₂ S + 7H ₂ O, and the reaction in the stripper 2 is MS + H ₂ O → MO + H ₂ S, The reaction in the catalyst regeneration device 3 is as follows: S + O ₂ → SO ₂ + SO ₃ 2SO ₂ + O ₂ → 2SO ₃ metal oxide (MO) + SO ₃ → MSO ₄ in coke.

In the above formula, M represents a metal.

The operating conditions at this time are as follows. Feed oil: Mixed oil of desulfurized vacuum gas oil (50%) and desulfurized atmospheric residue (50%) Feed oil S content: 0.28 wt% Weight space velocity: 25 hr-1 Catalyst / oil: 7 (weight ratio) Reaction temperature : 520 ° C Regenerator temperature: 680 ° C Stripping temperature: 520 ° C Coke on regenerated catalyst: 0.05wt%

In evaluating the catalyst performance, each of the catalyst compositions A to D was added with 1000 pp of nickel and vanadium, respectively.
m, deposited at 2000 ppm and then steamed to give a pseudo-equilibrium treatment. Specifically, after each catalyst was previously calcined at 600 ° C. for 1 hour, a predetermined amount of a toluene solution of nickel naphthenate and vanadium naphthenate was absorbed, and then 1
After drying at 10 ° C, baking at 600 ° C for 1.5 hours, then 8
After steaming at 10 ° C. for 12 hours, the cracking performance of heavy oil was evaluated using the apparatus shown in FIG.

Table 2 shows the obtained results. Table 2 also shows the results of analysis of SO ₂ , CO and CO _{2 in} the gas discharged from the flue gas outlet 17 in the regenerator after the operation has reached a steady state.

[0065]

[Table 2]

The catalyst compositions A and B for hydrocarbon fluid catalytic cracking containing manganese and zinc were subjected to quasi-equilibrium by hydrothermal treatment at a higher temperature even though they contained nickel and vanadium at high concentrations. Nevertheless high conversion
(Activity).

This indicates that the catalyst composition of the present invention is more excellent in metal resistance and hydrothermal resistance than conventionally known catalyst compositions. Further, the catalyst compositions A and B for the fluid catalytic cracking of hydrocarbons have low hydrogen and coke yields despite high conversion, while gasoline yield and liquid yields including gasoline and light cycle oil (LCO) The result was that the rate was high. Especially manganese-
The tendency was remarkable in the catalyst composition B having a high content of the zinc compound.

The octane number of the produced gasoline was substantially the same in the example and the comparative example. The above effect is due to the fact that the manganese-zinc compound contained in the catalyst composition for fluid catalytic cracking of hydrocarbons effectively captures and passivates metal contaminants, and adversely affects the metal contaminants, that is, decreases the activity due to zeolite destruction. And generation of hydrogen and coke due to dehydrogenation activity.

In order to further understand the above, it is additionally added that, when the conversion is high, the amount of gas and coke generated is increased, and the gasoline and LCO yields are increased. It is common knowledge in the art that the octane number increases in proportion to the conversion rate,
The hydrocarbon fluid catalytic cracking catalyst composition according to the present invention exhibits an effect exceeding this common sense.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of a commercially available manganese-zinc compound used in Examples.

FIG. 2 is an X-ray diffraction pattern of dimanganese trioxide powder used in a comparative example.

FIG. 3 shows Midg used in a catalyst evaluation test in Examples.
It is a schematic diagram of an et-2 pilot plant.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Reactor 2 Stripper 3 Catalyst regeneration device 4 Condenser 5 Fractionator 6 Receiver 7 Cat trap 8 Separator 9 Movable tube 10 Air cooling tube 11 N ₂ inlet 12 Feed oil inlet 13 N ₂ , H ₂ O outlet 14 N ₂ inlet 15 Air inlet 16 Transfer pipe 17 Smoke gas outlet

Claims (6)

[Claims] 1. A catalyst composition for fluid catalytic cracking of hydrocarbons, wherein (i) a crystalline aluminosilicate zeolite and (ii) a compound containing manganese and zinc are dispersed in (iii) an inorganic matrix. . 2. The compound (ii) containing manganese and zinc is a mixture of manganese oxide and zinc oxide, a composite oxide of manganese and zinc, manganese oxide and / or zinc oxide and the composite oxide The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1, which is a mixture of any of the following. 3. The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1, wherein (ii) the compound containing manganese and zinc is in the form of particles and has an average particle diameter of 60 μm or less. 4. The hydrocarbon fluidized contact according to claim 1, wherein the compound (ii) containing manganese and zinc is an oxide particle which can be detected by X-ray. Decomposition catalyst composition. 5. The catalyst composition for fluid catalytic cracking of hydrocarbons according to claim 1, further comprising (iv) activated alumina. (6) a crystalline aluminosilicate zeolite: 5 to 50% by weight (ii) a compound containing manganese and zinc: 0.1 to 50% by weight (iii) an inorganic matrix: 20 to 94.9% by weight The catalyst composition for fluid catalytic cracking of a hydrocarbon according to any one of claims 1 to 5, having a component composition in the range of: